Borate quaternary ammonium compounds derived from borate esters of amino secondary alkanols

ABSTRACT

QUATERNARY AMMONIUM SALTS OF BORATE ESTERS OF 1-DIALKYLAMINO-2-ALKANOLS ARE DISCLOSED; SUCH COMPOUNDS HAVING PARTICULAR UTILITY AS FABRIC SOFTENERS AND SANITIZERS.

United States Patent 3,660,459 BORATE QUATERNARY AMMONIUM COM- POUNDS DERIVED FROM BORATE ESTERS OF AMINO SECONDARY ALKANOLS Graham K. Hughes, Hackettstown, N.J., assiguor to Ashland Oil, Inc., Houston, Tex. No Drawing. Original application May 16, 1966, Ser. No. 550,157, now Patent No. 3,465,026, dated Sept. 2, 1969. Divided and this application Apr. 23, 1969, Ser.

Int. Cl. C070 141/04 US. Cl. 260-459 7 Claims ABSTRACT OF THE DISCLOSURE Quaternary ammonium salts of borate esters of l-dialkylamino-Z-al kanols are disclosed; such compounds having particular utility as fabric softeners and sanitizers.

CROSS REFERENCE TO RELATED APPLICATION This application is a division of Ser. No. 550,157, filed May 16, 1966, now Pat. No. 3,465,026.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to a process for the preparation of quaternary ammonium derivatives of borate esters of amino secondary alkanols. In a further aspect, it relates to the preparation of quaternary ammonium. salts of borate esters of 1-dialkylamino-2-alkanols,

Description of the prior art -In my application Ser. No. 5 0,101, filed May 16, 1966, now abandoned, there are disclosed borate esters of amino secondary alkanols and methods for preparing the same In accordance with the present invention, novel quaternary ammonium derivatives of the aforesaid borate esters and processes for the preparation thereof are disclosed and claimed.

SUMMARY OF THE INVENTION In accordance with this invention, a new class of compounds is provided, which compounds are the quaternary ammonium salts of borate esters of amino-substituted secondary alkanols, said compounds having the general formulae:

R-CH-O B-O-B o..c

R il 9 iloo c1-I N.X err nds it A where R; and R are alkyl groups having 1 to 22 carbon atoms, preferably 1 to 8 carbon atoms, or are lower alkyl groups substituted with aryl, cyclo :alkyl, cyclo alkenyl, allraryl, alkylcycloalkyl or alkylcycloalkenyl groups having -6 to 10 carbon atoms, or R and R together with the nitrogen atom form a heterocyclic nitrogen group having 2 to 6 ring carbon atoms; and R is an alkyl group, either straight or branched chain having from 6 to 22 carbon atoms, preferably 9-16 carbon atoms, or R is an alkoxy-substituted alkyl having from 822, preferably from 9-16 carbon atoms; R is a hydrocarbon radical selected from the group consisting of alkyl of 1 to carbon atoms or aryl, e.g., benzyl, and X is a quaternizing anion, e.g., chloride, bromide, iodide, sulfate, and the like.

The borate esters can be prepared by reacting aminosubstituted secondary alkanols with boric acid as disclosed in application Ser. No. 550,101, supra. Depending upon the mole ration of alkanol to acid, the borate esters having the following general formulae are produced:

It will be apparent that the esters corresponding to Formula IV above can be quaternized to obtain the compounds corresponding to Formula I. Further, esters V and W can be quaternized to obtain the compounds structurally shown by Formulas II and III, respectively.

The aminosubstituted secondary alkanols can be prepared by reacting 1,2-epoxides of long-, straight-, or branched-chain, terminally unsaturated mono-olefins,

such as those having 8 to 24 carbon atoms, preferably 11 to 18 carbon atoms, per molecule, with a secondary amine or secondary hydroxy amine, such as dimethylamine, diethylamine, dipropylamine, dioctylamine, methyl ethylamine, ethyl butylamine, ethyl ethanolamine, diethanolamine, diisopropanolamine, diglycerolamine, cyclohexylmethylamine, morpholine, piperidine, 3,5-bis(hydroxymethyDmorpholine, pyrrolidine, pyrrole, azepine, aziridine, azetidine, hexahydroazepine, methyl benzylamine, ethylphenethylamine, methyl l-naphthalene methylamine, and the like.

The 1,2-epoxides used in preparing such amino secondary alkanols can, in turn, be prepared by the epoxidation of said terminal olefins with an aliphatic peracid, such as peracetic acid. Such terminal olefins can be used singly or in admixture, and they can be straight-chain or branchedchain terminal olefins. Long, straight-chain terminal monoolefins can be obtained from petrochemical sources, for example, by cracking of petroleum waxes or by polymerization of ethylene using Ziegler catalysts such as trialkylaluminum. Representative l-olefins which can be used to prepare the 1,2-epoxide precursors include l-decene, 1- hendecene, l-dodecene, l-hexadecene, l-octadecene, 1- eicosene, and the like, including mixtures thereof-Table I sets forth a description and specifications for some long chain, terminal mono-olefin mixed fractions commercially available from petrochemical sources which can be epoxidized to prepare the precursor 1,2-epoxides of said amino secondary alkanols. Where such terminal mono-olefins are used as the initial precursors of the amino-substituted alkanols, the borate esters, prepared in this invention, will be mixtures of said esters, the various carbon chain lengths of the beta-substituted group attached to the nitrogen atom corresponding to that of the olefin fraction.

TABLE I n-Cu Cir- Cir-C10 Cit-C Gib-C1! (320+ Total straight chainalpha olefins percent-.. 87 87 93.5 86 88.8 69 Carbon 0.

distributing,

percent:

n- Specific gravity,

20 lml 3-hydroxybutyl dimethylamine, 9-hydroxystearyl dimethylamine, l-dimethylamino-Z-decanol, 1-dimethylamino-2-hendecanol, 1-fiN-methyl-N-ethy1amino)-2-dodecanol, 1-dipropylamino-2-tridecanol, 1-(N-ethyl-N-butyl)-amino-2-tetradecanol, l-(N-pentyl-N-hexyl) amino-Z-pentadecanol, l-(N-methyl-N-heptyl) amino-Z-hexadecanol, '1-(N-heptyl N-octyD-amino-Z-octadecanol, 1-dioctylamino-2-eicosanol, 1-dibutylamino-2-heneicosanol,

l -dirnethyl amino-2-nonadecanol,

1-diethylamino-Z-eicosanol, l-dipentyl-amino-Z-docosanol, l-(N-methyl-N-ethyl) amino-2-tricosanol, l-dioctylamino-Z-tricosanol N-(2-hydroxydecyl) pyrrolidine, N-(Z-hydroxyoctyl)-piperidine, N-(2-hydroxyeicosyl) decahydroquinoline,

l- (bis-2-hydroxyethyl) amino-Z-decanol,

lmethyl-Z-hydroxyethyl) amino-2-dodecanol, l-(bis-2-hydroxypropyl)aminoZ-tetradecanol, 1- (methyl-Z-hydroxypropyl -amino-2-octadecanol, l-(N-methyl-N-butyl) amino-2-eicosanol,

and the like, including mixtures thereof.

The quaternary ammonium salts are prepared according to this invention by quaternizing said borate esters of said amino-substituted alkanols at temperatures in the range of 40 to C. with a quaternizing agent, such as methyl chloride, benzyl chloride, dodecenyl chloride, methyl sulfate, and the like. In general, the quaternizing agent is an alkyl, chloride, bromide, iodide or sulfate, an arylalkyl halide, an alkyl ester of an aromatic sulfonic acid or the like. In this process the quaternizing agent is, preferably, slowly added to a heated mixture of the borate ester, water and a solvent, such as a lower alkanol, e.g., methanol, ethanol, propanol, or butanol. The amount of quaternizing agent added is usualy about 1 to 25% in excess of the stoichiometric amount. The quaternaries are generally water-soluble and can be used, for example, as fabric softeners. Further, the quaternaries, especially those obtained when an aromatic halide, e.g., benzyl chloride, is used as the quaternizing agent, are useful as disinfectants and/or sanitizers.

Representative quaternary ammonium salts of the borate esters of amino-secondary alkanols which can be made according to this invention, include the quaternary ammonium salts of the borate esters of any of the aforementioned amino-secondary alkanols, such as the quaternary ammonium chloride of the borate ester of betahydroxy-C, -alky1dimethylamine.

The following working examples are illustrative of the best mode contemplated for carrying out the present invention.

EXAMPLE I In this example grams of the borate ester of betahydroxy-C -al'kyl dimethylamine (prepared by reacting 3 moles of the hydroxyamine with 1 mole of boric acid) were reacted With 51.7 grams of benzyl chloride in an isopropanol-water system to prepare the benzyl chloride quaternary ammonium salt.

To obtain the quaternary, the borate ester, 40.3 grams of isopropanol and 10.1 grams of water were charged to a reactor. The reactor and its contents were then heated to 6070 C. after which 51.7 grams of benzyl chloride were dripped in over a one-half hour period. The reaction mixture was then held at 65 C. for 2 days. The reaction was substantially quantitative, there being 0.57% free amine in the product.

The quaternary ammonium compound is readily dispersed in cold water and, when employed at a 0.1% level in the rinse water of a washing machine cycle, improves the fiufiiness and softness of towels to a greater extent than similarly treated towels employing a commercially available fabric softener. Further, the quaternary shows disinfecting and/or sanitizing properties.

EXAMPLE II In this example, 79.5 grams of the borate ester used in Example I were reacted with 73.7 grams of dodecenyl chloride in an isopropanol-water system to prepare the dodecenyl chloride quarternary ammonium Salt of the borate ester. The procedure was similar to that of Example I. 3.16 grams of isopropanol and 9.8 grams of water were used. After 4 days the reaction was complete, these being 0.89% free amine in the product. This quaternary shows similar fabric-softening and sanitizing properties.

EXAMPLE III In this example, 100 grams of the borate ester of betahydroxy-C -dimethylamine (prepared by reacting 3 moles of the hydroxy amine with 1 mole of boric acid) were reacted with 48.6 grams of benzyl chloride to prepare the quaternary ammonium salt in a manner quite similar to that used in Example I. 39.6 grams of isopropanol and 99 grams of water were used as the solvent system. After 2 days, at 50 C., the reaction was substantially complete, there being 0.53% free amine in the product. The quaternary ammonium compound showed surprising germicidal properties when used as a fabric softener.

EXAMPLE IV In this example, 100 grams of the borate ester used in Example III were reacted with 84.2 grams of dodecenyl chloride to prepare the dodecenyl chloride quaternary ammonium salt of the ester. The procedure used was similar to that of Example I. The solvent system used comprised 12.3 grams of water and 49.1 grams of isopropanol. The reaction mixture was held at 60 C. for about 12 hours at which time the percentage of free amine was about The quaternary so obtained showed excellent germicidal activity and is used as a fabric softener.

EXAMPLE V In this example, 165 grams of the borate ester of betahydroxy-C -alkyl dimethylamine (prepared by reacting 3 moles of the hydroxy amine with 1 mole of boric acid) were reacted with 64.2 grams of methyl sulfate, by a procedure similar to that observed in the previous examples, to obtain the methyl sulfate quaternary ammonium salt of the ester. The solvent System comprised 61.2 grams of isopropanol and 15.3 grams of water. The reaction mixture was held at 60-70 C. for 2 days after which time the percent total amine nitrogen (T.A.N.) was 0.018% and the percent free amine was 0.417%. Accordingly, the reaction was substantially complete.

The quaternary so obtained is readily dispersed in cold water, and, when employed at a 0.1% level in the rinse water of a washing machine cycle, improves the fluflines and softness of towels to a greater extent than similarlytreated towels employing a commercially-available fabric softener.

EXAMPLE VI In this example, 128 grams of the borate ester of betahydroxy-C; -a1kyldimethylamine (prepared by reacting 1 mole of the hydroxy amine with /2 mole of boric acid) were reacted with 193 grams of dodecenyl chloride. The solvent system comprised 256 grams of isopropanol and 64 grams of water. After about 2 /2 hours the reaction was complete in that the total amine nitrogen was approximately zero.

The quaternary so obtained is evaluated as a fabric softener and shown to possess good softening properties and compatibility with zinc nitrate.

6 I clarm: 1. A class of compounds having the general formula:

where R is an alkyl group having 6 to 22 carbon atoms; R and R are alkyl groups having 1 to 8 carbon atoms; R is dodecenyl, benzyl or alkyl having not in excess of 15 carbon atoms and X is an anion selected from the group consisting of chloride, bromide, iodide and methyl sulfate.

2. Quaternary ammonium compounds according to claim 1 where R and R are methyl groups.

5. Quarternary ammonium compounds according to clarm 2 where 'R is an alkyl group having 9 to 16 carbon atoms.

4. Quarternary ammonium compounds according to claim 1 where X is a chloride or a methyl sulfate anion.

5 Quarternary ammonium compounds according to clarm 4 where R is benzyl.

6 Quaternary ammonium compounds according to clarm 4 where R is dodecenyl.

7 Quaternary ammonium compounds according to clarm 4 where R is methyl.

References Cited UNITED STATES PATENTS 2,259,175 10/1941 Paul 260-462 X 3,072,737 l/1963 Chen 260-462 X LEON ZITVER, Primary Examiner L. B. DECRESCENTE, Assistant Examiner US. Cl. X.R. 260462 R 

